Phosphoric (-phosphonic) and thiono-phosphoric (-phosphonic) acid esters



United States Patent Int. Cl. C07d 55710; A0111 9/22 US. Cl. 260-448 9Claims ABSTRACT OF THE DISCLOSURE (Alkyl, phenyl and0-alkyl)-O-alkyl-O-(benZo-1,2,4- triazin-3-yl)-(phosphoric andphosphonic) and thiono- (phosphoric and phosphonic) acid esters whichpossess arthropodicidal, especially acaricidal and insecticidal,properties and which may be produced by reacting the correspondingphosphoric (phosphonic) and thiono-phosphoric (-ph0sphonic) acid esterhalide with 3-hydroxybenzo-l,2,4-triazine.

The present invention relates to and has for its objects the provisionfor particular new phosphoric (phosphonic) and thiono-phosphoric(-phosphonic) acid esters of 3- hydroxy-benzo-1,2,4triazines whichpossess arthropodicidal, especially insecticidal and acaricidal,properties, active compositions in the form of mixtures of suchcompounds with solid and liquid dispersible carrier vehicles, andmethods for producing such compounds and for using such compounds in anew way especially for combating pests, e.g., arthropo ds,-with otherand further objects becoming apparent from a study of the withinspecification and accompanying examples.

In German Patent 927,270 thiophosphoric acid esters ofN-methyl-benzaimides are already described, while there are known fromGerman Patent 1,115,738, openchain and cyclicquinoxalino-2,3-thiophosphoric acid esters which, by reason of theirgood insecticidal and acaricidal properties, are used as pesticides.These lastmentioned esters, however, either have the disadvantage thatthey are less effective against resistant spider mites or that theirproduction presents technological difiiculties.

It has been found in accordance with the present invention that theparticular new phosphoric (phosphonic) and thjionophosphoric(-phosphonic) acid esters of 3-hydroxybenzo -1,2,4-triazi.nes, i.e.(alkyl, phenyl and O- alkyl)'-O-alkyl-O-(benzo 1,2,4triazin-3-yl)-(phosphoric and phosphonic) and thiono-( phosphoric andphosphonic) acid'esters, having the formula and sulfur, exhibit strongarthropodicidal, especially insecticidal and acaricidal, properties.

It has been furthermore found in accordanceiwith the present inventionthat a versatile and smooth process for the production of the particularnew phosphoric and phosphonic and thiono-phosphoric and -phosphonic acidesters of 3-hydroxy-benzo-1,2,4-triazines of Formula I above infavorable yields may be provided, which comprises reacting3-hydroxy-(benzo-1,2,4-triazine) having the formula N no-f W N (Ha) withthe corresponding phosphoric, phosphonic or thionophosphoric(-phosphonic) acid ester halide having the formula RO\ %X P R Hal (11b)in which R, R and X are the same as defined above, and Hal is a halogenatom, especially chloro or bromo.

The particular new esters of Formula I above exhibit, as has furtherbeen found, strong insecticidal and acaricidal properties. They possessan excellent activity against eating and sucking insects, ticks and, inparticular, against resistant spider mites. These compounds are invthisrespect clearly superior to the known products of comparableconstitution and type of activity and therefore the instant compoundsrepresent a genuine enrichment of the art.

The process for producing the particular new compounds according to thepresent invention is illustrated by the following typical reactionscheme:

(IIb) (Ha) (I) the symbols R, R, X and Hal being the same as definedabove.

. The 3-hydroxy-benzo-l,2,4-triazine and the corresponding phosphorusacid ester halides necessary as starting materials for carrying out theprocess according to the present invention are known from theliterature.

The production process according to the present invention is carried outpreferably in the presence of suitable inert solvents (this termincludes mere diluents). As such, practically all inert organic solventsor mixtures thereof are suitable, such as hydrocarbons, e.g., benzine,benzene, toluene, chlorobenzene, xylene; ethers, for example diethyl anddibutyl ether, dioxan; ketones, e.g., acetone, methylethyl,methylisopropyl and methylisobutyl ketone. However, particularly goodresults have been obtained with low-boiling aliphatic alcohols, forexample methanol and ethanol, and even better results with nitriles,e.g., acetonitrile and propionitrile, and dimethyl formamide.

Moreover, the reaction according to the instant process is preferablycarried out in the presence of acid acceptors. For this purpose,practically all customary acidbinding agents can be used. Particularlysuitable are: alkali metal alcoholates and carbonates, such as potassiumand sodium methylate or ethylate, sodium and potas- 3 sium .carbonate,and tertiary aromatic or heterocyclic amines, e.g., triethyl amine,dimethyl aniline or pyridine.

The reaction temperature can be varied within a fairly wide range. Ingeneral, the reaction is carried out at substantially between about 20to 120 C. (or the boiling point of the mixture), preferably at about 40to 80 C. The starting materials to be reacted according to such process,as well as the auxiliary materials (acid-binding agents), are, ingeneral, used in stoichiometric amounts. After combining the startingcomponents it is advantageous, in order to complete the reaction tocontinue heatmg the mixture for a longer period (about /2 to 3 hours),optionally with stirring. With this method of working, the products areobtained with outstanding yields and in excellent purity.

The particular new phosphoric and thiono-phosphoric (-phosphonic) acidesters of 3-hydroxy-benzo-1,2,4-triazine which are obtainable accordingto the instant process are obtained in most cases as colorless crystalswith sharp melting points which, if necessary, can readily be furtherpurified by recrystallization from the usual sol vents. Some of theinstant products are obtained in the form of colorless toyellow-colored, viscous, water-insoluble oils Which cannot be distilledwithout decomposition but which can be freed from the last volatilecomponents by so-called slight distillation, i.e., longer heating tomoderately elevated temperatures under reduced pressure, and in this waybe purified. For their more precise characterization, the determinationof the refractive index can be used.

As already mentioned above, the instant compounds are distinguished byoutstanding insecticidal and acaricipounds which can be preparedaccording to the present invention can be used with success in plantprotection for the control of noxious sucking and eating insects andDiptera as well as against mites (Acarina).

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (.Rhopalosiphum path),the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphumsolanifolii), the currant gall aphid (Cryptomyzus korschelti), the mealyapple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterusarundinis) and the cherry black-fly (Myzus cerasi); in addition, scalesand mealybugs (Coccina), for example the oleander scale (Aspidiotuslzederae) and the soft scale (Lecanium lzesperidum) as well as the grapemealybug (Pseudococcus maritimus); thrips (Thysanoptera), such asHercinothrips femoralis, and bugs, for example the beet bug (Piesmaquadrata), the cotton bug (Dysdercus intermedius), the bed bug (Cim'exlectularius), the assassin bug (Rhodnius prolixus) and Chagas bug(Triatoma infestans) and, further, cicadas, such as Euscelis bilobatusand Nephoteltix bipunctatus, and the like.

In the case of the biting insects contemplated herein, above all thereshould be mentioned butterfly caterpillars (Lepidoptera) such as thediamond-back moth (Plmella maculipermis), the gipsy moth (Lymantriadispar), the brown-tail moth (Euproctz's chrysorrhoea) and tentcaterpillar (Malacoso ma neustria); further, the cabbage moth (Mamestrabrassicae) and the cutworm (Agrotis segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobia brumata), thegreen oak tortrix moth (T ortrix viridana), the fall armyworm (Laphygmfrugiperda) and cotton worm (Prodenia litura), the ermine moth(Hyponomeuta padella), the Mediterranean flour moth (Epestia kuhniella)and greater Wax moth (Galleria mellonella); and the like. Also to beclassed with the biting insects contemplated herein are beetles(Coleoptera), for example the granary 4 weevil (Sitophilz'usgranarius-Calandra granaria), th Colorado beetle (Leptinotarsadecemlineata), the "dock beetle (Gastrophysa viridula), the mustardbeetle (Phaedon cochelearia), the blossom beetle (Meligethes aeneus),the raspberry beetle (Byturus tomentosus), the bean weevil(Bruchidius-Acanthoscelides obtectus), the leather beetle (Dermestesfrischi), the khapra beetle (Trogoderma granarium), the flour beetle(Tribolium castaneum), the northern corn billbug (Calandra or Silophiluszeamais), the drugstore beetle (Stego bium paniceum), the yellowmealworm (Tenebrio molitor) and the saw-toothed grain beetle(Oryzaephilius surinamensis), but also species living in the soil, forexample wireworms (Agriotes spec.) and larvae of the cockchafer(Melolontha melolontha); cockroaches, such as the German cockroach(Blattela germanica), American cockroach (Periplaneta americana),Maderia cockroach (Laucophaea or Rhyparobia madeirae), Orientalcockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus)and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the housecricket (Gryllus domesticus); termites such as the eastern subterraneantermite (Reticulitermes flavipes) and Hymenoptera such as ants, forexample the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly(Ceratitis capitata), the house fly (Musca domestica), the little housefly (Fannz'a canicularis), the black blow fly (Phormia aegina) andbluebottle fly (Calliphara erythrocephala) as Well as the stable fly(Stomoxys calcitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypti), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius- T etranychus althaeae or T etranychusurlicae) and the European red mite (Paratetranychus pilosus-panonychusulmi), blister mites, for example the currant blister mite (Eriophyesribis) and tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornithodorus moubata); and the like.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withdiluents or extenders, i.e., dispersible carrier vehicles, such assolutions, emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with dispersible liquid diluent carriers and/or dispersiblesolid carriers optionally with the use of carrier vehicle assistants,e.g., surface-active agents, including emulsifying agents and/ ordispersing agents, whereby, for example, in the case where water is usedas diluent, organic solvents may be added as auxiliary solvents (cf.Agricultural Chemicals, March 1960, pages 35-38). The following may bechiefly considered for use as carrier vehicles for this purpose:dispersible liquid diluent carriers, including inert organic solvents,such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.),halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), paraflins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.), and/ or water; as Wellas dispersible finely divided solid carriers, such as ground nat uralminerals (e.g. kaolins, alumina, silica, chalk, i.e.,

calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals(e.g., highly dispersed silicic acid, silicates, e.g., alkali silicates,etc.); whereas the following may be chiefly considered for use ascarrier vehicle assistants, e.g., surface-active agents, for thispurpose: emulsifying agents, such as nonionic and/or anionic emulsifyingagents (e.g., polyethylene oxide esters of fatty acids, polyethyleneoxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc.,and especially alkyl arylpolyglycol ethers, magnesium stearate, sodiumoleate, etc.); and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/ or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides,insecticides, fungicides, herbicides, bactericides, etc., if desired, orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95% by weight, andpreferably 0.590% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.00001 and 20%, preferably 0.0l-5%, byweight of the mixture. Thus, the present invention contemplates overallcompositions which comprise mixtures of a dispersible carrier vehiclesuch as (1) a dispersible inert finely divided carrier solid, and/or (2)a dispersible carrier liquid such as an inert organic solvent and/ orwater preferably including a surface-active amount of a carrier vehicleassistant, e.g. surface-active agent, such as an emulsifying agentand/or a dispersing agent, and an amount of the active compound which iseffective for the purpose in question and which is generally betweenabout 0.00001 and 95%, and preferably 0.01-95 by weight of the mixture.

The active compounds can also be used in accordance with the well knownultra-loW-volume process with good success, i.e., 'by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in extremelyfinely divided form, i.e., mist form, for example by airplane cropspraying techniques. Only a few liters/ hectare are needed, and oftenamounts up to about 1 quart/acre, preferably 2-l6 fluid ounces/acre, aresufficient. In this process it is possible to use highly concentratedliquid compositions with said liquid carrier vehicles containing fromabout 40 to about 95% by weight of active compound or even the 100%active substance alone, e.g., about 40-100% by weight of the active compound.

In particular, the present invention contemplates methods of selectivelycontrolling or combating pests, e.g. arthropods, i.e., insects andacarids, and more particularly, methods of combating at least one ofinsects and acarids which comprises applying to at least one ofcorrespondingly (a) such insects, (b) such acarids, and (c) thecorresponding habitat, i.e., the locus to be protected, acorrespondingly combative amount, i.e., an arthro' podicidally,especially insecticidally or acaricidally, effective amount of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring, and thelike.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture 6 with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The outstanding activity of the particular new compounds of the presentinvention is illustrated Without limitation by the following examples:

EXAMPLE 1 Tetranychus test.-Solvent: 3 parts by weight acetone;emulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of the particular active compound, 1part by weight of such active compound is mixed with the stated amountof solvent containing the stated amount of emulsifier and theconcentrate so obtained is diluted with water to the desired finalconcentration.

Beanplants (Phaseolus vulgaris), which have a height of approximately10-30 cm., are sprayed with the active compound preparation untildripping wet. These bean plants are heavily infested with spider mites(Tetranychus telarius) in all stages of development.

After the specified period of time, the effectiveness of the givenactive compound preparation is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:means that all the spider mites are killed whereas 0% means that none ofthe spider mites are killed.

The particular active compounds tested, their concentrations, theevaluation time and the results obtained can be seen from the followingTable 1:

TABLE 1 Active compound (constitution) in percent after 2 days 0 S H 0 1100 (A) (C2H50)2PSCHr-I| l I 0 (Known comparative preparation) Q N(III1) P-o 0.1 100 I 0.01 70 2 50 N \i N (1V1) PO(/ 0. 1 100 0. 01 100O2H5O n N\ (v1) (CH5O) POf o 1 100 o 01 as N EXAMPLE 2 Myzus test(contact action) .Solvent: 3 parts by weight acetone; emulsifier: 1 partby weight alkylaryl polyglycol ether.

To produce a suitable preparation of the particular active compound, 1part by weight of such active compound is mixed with the stated amountof solvent containing the stated amount of emulsifier and the resultingconcentrate is diluted with water to the desired final concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested withpeach aphids (Myzus persicae) are sprayed with the given active compoundpreparation until dripping wet.

After the specified period of time, the degree of destruction isdetermined as a percentage: 100% means that all the aphids are killedwhereas means that none of the aphids are killed.

The particular active compounds tested, their concentrations, theevaluation time and the results obtained can be seen from the followingTable 2:

TABLE 2 Concen- Degree of tration of destruction active in percentcompound after 24 Active compound (constitution) in percent hours 1 S u(A) (oznfionr-s-onz-l r i 8: 28 N (Known comparative preparation) KE N1112 P-o 0 1 100 1 0. 01 100 CgHaO N ozflifi N (IVg) P-O 0.1 100 0. 01100 CaHsO N 0. 001 80 i N v1. unmonr-o- 0.1 100 l 0.01 100 N I] N (v0(c.n.o).P-o- 0.1 100 0. 01 100 N 0. 001 50 EXAMPLE 3 Plutellatest-Solvent: 3 parts by weight acetone; emulsifier: 1 part by weightalkylaryl polyglycol ether.

To produce a suitable preparation of the particular active compound, 1part by weight of such active compound is mixed with the stated amountof solvent containing the stated amount of emulsifier and the resultingconcentrate is diluted with water to the desired final concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the given activecompound preparation until dew moist and are then infected withcaterpillars of the diamondback moth (Plutella maculipennis).

After the specified period of time, the degree of destruction isdetermined as a percentage: 100% means that all the caterpillars arekilled whereas 0% means that none of the caterpillars are killed.

The particular active compounds tested, their concentrations, theevaluation time and the results obtained can be seen from the followingTable 3:

TABLE 3 Concentration of Degree of active destruction compound inpercent Active compound (constitution) in percent after 3 days w N 111.P-0- 0.1 100 1 0.01 100 021150 N CaH5\ISI N (1V P-Q- 0.1 100 1 0 01 100021150 N 0.001 100 s I] N v12 (CZH5O)QPO(/ 0.1 100 0. 01 100 N i 0.001

0 II N or.) winsonr-o-f 0.1 100 0. 01 100 N i 0.001

The following further examples illustrate, without limitation, theprocess for producing the particular new compounds of the presentinvention.

EXAMPLE 4 T l N 002115 \N// (V4) A mixture of 45 g. (0.3 mol)3-hydroxy-benzo-l,2,4- triazine, 42 g. potassium carbonate and 750 ml.acetonitrile is heated to the boil for 1 hour. 52 g.0,0-diethylphosphoric acid ester chloride are then added dropwise to thereaction mixture at boiling temperature; the latter is heated for afurther 3 hours under reflux, and the mixture is cooled and poured intoWater. The product separating in oil form is taken up in benzene, thebenzene solution is washed with 1 N KOH and then washed several timeswith water, the organic phase is dried over sodium sulfate and freedfrom solvent under reduced pressure. By recrystallization of the residuefrom a benzene-ligroin mixture there are obtained 76 g. (90% of thetheory) of 0,0-diethy1-O-(benZo-1,2,4-triazin-3yl)- phosphoric acidester of meling point 46 to 47 C.

Analysis.Calculated for C H N O P (molecular weight 283.2) (percent): N,14.83; P, 10.96. Found (percent): N, 14.93; P, 11.19.

EXAMPLE 5 S OCzHa N N (v13) 44 g. (0.3 mol)3-hydroxy-benzo-1,2,4-triazine and 31 g. triethyl amine are dissolved at50 to 60 C. in ml. dimethyl form-amide, and 57 g. (0.3 mol)0,0-diethylthionophosphoric acid ester chloride are added to thissolution. After the exothermic reaction which sets in has subsided (thereaction is caused to proceed at 60 to 70 C. by mild external cooling ofthe vessel), the mixture is stirred for a further 2 hours at thistemperature. The working up of the reaction mixture takes place asdescribed in the case of Example 4. 64 g. (75% of the theory) of0,0-diethyl-O-(benzo-1,2,4-triazin-3-yl)-thionophosphoric acid ester areobtained as semi-solid product which, after recrystallization from abenzene/petroleum ether mixture, melts at 56 C.

Analysis.-Calculated for C H N O PS (molecular weight 299.3) (percent):N, 14.04; P, 10.35; S, 10.7. Found (percent): N, 13.65; P, 10.22; S,10.44.

EXAMPLE 6 N on, 1114) EXAMPLE 7 As described in Example 4 or analogouslyas in Example 5, by reaction of 44 g. (0.3 mol) 3-hydroxy-benzo-1,2,4-triazine and 52 g. ethyl-thionophosphonic acid ethyl esterchloride there are obtained 43 g. (51% of the theory) of pureethyl-thionophosphonic acid O-ethyl-O- (benzo-1,2,4-triazin-3-yl) esterof melting point 85 C. (from benzene-ligroin).

Analysis.Calculated for C H N O PS (molecular weight 283.3) (percent):N, 14.83; P, 1 0.94; S, 11.32. Found (percent): N, 14.83; P, 10.90; S,11.56.

EXAMPLE 8 According to the method of Example 4, from 44 g. (0.3 mol)3-hydroxy-benzo-1,2,4-triazine and 66- g. (0.3 mol)phenyl-thionop-hosphonic acid O-ethyl ester chloride there are obtained65 g. (65% of the theory) of the phenyl-thionophosphonic acidO-ethyl-O-(benzo-1,2,4-triazin- 3-yl)ester with the refractive index n1.6235.

Advantageously, in accordance with the present invention, in theforegoing formulae:

R represents:

alkyl having 1-4 carbon atoms such as methyl to tert.- butyl inclusive,especially methyl, ethyl, nand iso-propyl, n-, isoand s-butyl, and thelike, and more particularly alkyl having 1-3 or 1-2 carbon atoms,preferably ethyl;

R represents:

(VII!) alkyl having 1-4 carbon atoms such as methyl to tert.-

butyl inclusive as defined above, and more particularly alkyl having 1-3or 1-2 carbon atoms; or

alkoxy having 1-4 carbon atoms such as methoxy to tert.-

butoxy inclusive, especially methoxy, ethoxy, nand iso-propoxy, n-,isoand s-butoxy, and the like, and

more particularly alkoxy having 1-3 or 1-2 carbon atoms, preferablyethoxy; or phenyl; and

X represents:

oxygen or sulfur, especially sulfur.

Preferably, R is C alkyl, R is C alkyl or C alkoxy; and X is oxygen orsulfur, most preferably sulfur. In particular, R is methyl or ethyl, Ris methyl, ethyl, methoxy or ethoxy; and X is oxygen or sulfur,especially sulfur.

The instant compounds particularly contemplate C alkyl-O-C alkylandO,O-di-C alkyl-O-(benzo-1,2, 4-triazin-3-yl)-phosphoric andthiono-phosphoric (-phosphonic) acid esters.

It will be realized that all of the foregoing compounds contemplated bythe present invention possess the desired selective pesticidal,especially arthropodicidal, i.e., insecticidal or acaricidal, propertiesfor combating insects and acarids, and that such compounds have not onlya very slight toxicity toward warm-blooded creatures, but also aconcomitantly low phytotoxicity.

As may be used herein, i.e., both in the specification and claims, theterms arthropod, arthropodicidal and arthropodicide contemplatespecifically both insects and acarids. Thus, the insects and acarids maybe considered herein collectively as arthropods to be combated inaccordance with the invention, and accordingly the insecticidal and/oracaricidal activity may be termed arthropodicidal activity, and theconcomitant combative or effective amount used will be anarthropodicidally effective amount which in effect means aninsecticidally or acaricidally elfective amount of the active compoundfor the desired purposes.

What is claimed is:

1. Phosphorus-acid ester of benzo-1,2,4-triazine having the formula R isC alkoxy, and X is selected from the group consisting of oxygen andsulfur.

4. Ester according to claim 1 wherein R is C alkyl, R is C alkyl, and Xis sulfur.

5. Ester according to claim 1 wherein such compound is methyl O ethyl O(benzo 1,2,4 triazin 3 yl)- thionophosphonic acid ester having theformula 6. Ester according to claim 1 wherein such compound 7. Esteraccording to claim 1 wherein such compound is 0,0 diethyl O (benzo 1,2,4triazin 3 yl) phosphoric acid ester having the formula 8. Esteraccording to claim 1 wherein such compound is 0,0 diethyl O (benzo 1,2,4triazin 3 yl)- thionophosphoric acid ester having the formula 9. Esteraccording to claim 1 wherein such compound is phenyl O ethyl O (benzo1,2,4 triazin 3 y1)- thionophonic acid ester having the formulaReferences Cited UNITED STATES PATENTS 2,489,353 11/1949 Wolf et al260248 2,489,358 11/1949 Wolf et a1 260248 OTHER REFERENCES Jiu et a1.:J. Org. Chem, v01. 24, pp. 813-8 (1959).

HENRY R. JILES, Primary Examiner J. M. FORD, Assistant Examiner US. Cl.X.R. 424249

